CN1360682A - Polarizer comprising dye - Google Patents

Polarizer comprising dye Download PDF

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Publication number
CN1360682A
CN1360682A CN00810096A CN00810096A CN1360682A CN 1360682 A CN1360682 A CN 1360682A CN 00810096 A CN00810096 A CN 00810096A CN 00810096 A CN00810096 A CN 00810096A CN 1360682 A CN1360682 A CN 1360682A
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China
Prior art keywords
general formula
polarization plates
polarizing coating
water
liquid crystal
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CN00810096A
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CN1175289C (en
Inventor
大矶昭二
石井久美子
梶原义孝
田部井达
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Priority claimed from JP11200435A external-priority patent/JP2001027708A/en
Priority claimed from JP21114899A external-priority patent/JP4162334B2/en
Priority claimed from JP23405899A external-priority patent/JP4162336B2/en
Application filed by Nippon Kayaku Co Ltd filed Critical Nippon Kayaku Co Ltd
Publication of CN1360682A publication Critical patent/CN1360682A/en
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
    • C09B31/06—Disazo dyes from a coupling component "C" containing a directive hydroxyl group
    • C09B31/068—Naphthols
    • C09B31/072—Naphthols containing acid groups, e.g. —CO2H, —SO3H, —PO3H2, —OSO3H, —OPO2H2; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/16—Trisazo dyes
    • C09B31/20—Trisazo dyes from a coupling component"D" containing a directive hydroxyl group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/16—Trisazo dyes
    • C09B31/22—Trisazo dyes from a coupling component "D" containing directive hydroxyl and amino groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/30—Other polyazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/24—Disazo or polyazo compounds
    • C09B45/28—Disazo or polyazo compounds containing copper
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/06—Polyhydrazides; Polytriazoles; Polyamino-triazoles; Polyoxadiazoles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/03—Viewing layer characterised by chemical composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/03—Viewing layer characterised by chemical composition
    • C09K2323/031—Polarizer or dye
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/05—Bonding or intermediate layer characterised by chemical composition, e.g. sealant or spacer
    • C09K2323/057—Ester polymer, e.g. polycarbonate, polyacrylate or polyester
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers

Abstract

This invention relates to a polyvinyl alcohol type polarizing film or plate which comprises a water-soluble dye having the formula (1) in a free acid form or a copper complex salt thereof. The said polarizing plate has excellent polarizing performance capability and durability, and is suitably used for the green channel of a liquid crystal projector when B in formula (1) is a benzoylamino group and the water-soluble dye has awave length for maximum absorption ( lambda max) of 520 nm or more and less than 580nm.

Description

Polarizer comprising dye
Technical field
The present invention relates to a kind of new polyvinyl alcohol (PVA) type polarization plates.Further, the present invention relates to a kind of polarization plates that is used for liquid crystal projection apparatus and color liquid crystal projector, more particularly, the present invention relates to a kind of be used to liquid crystal projection apparatus that has good brightness and polarization property and be applicable to green channel and the polarization plates of using the color liquid crystal projector of polarization plates.
Background technology
Polarization plates with light transmission and protecting screen function is the basic composition unit of liquid crystal display (LCD), uses with the liquid crystal with light switch function.The use of LCD expands to auto navigation that notebook personal computer, word processor, liquid crystal projection apparatus, LCD TV device, indoor and outdoors use and measuring equipment etc. from the small-size equipment of starting stage such as pocket calculator and wrist-watch, they are from low temperature to high temperature, use in the wide working range from the low humidity to the high humility, therefore need have the high polarization property and the polarization plates of excellent durability.
Present polarization plates prepares as the polarizer by adding iodine or two look dyestuffs in the film of the stretching, extension and the polyvinyl alcohol (PVA) or derivatives thereof of orientation.Also can prepare polyene or dewater polyvinyl alcohol (PVA) type film then perhaps that directional trend prepares from polyene type film by dehydrochlorination by polychloroethylene film.Wherein use iodine to have good initial polarization property as the iodine type polarization plates of the polarizer, but to water and thermo-responsive, and when long-time use the under high temperature and high humidity, have endurance issues.In order to improve permanance, considered to handle or use the method for the polymer film of low-moisture permeability, but still be not enough to deal with problems as diaphragm with formalin or borated aqueous solution.On the other hand, use two look dyestuffs to compare with iodine type polarization plates and have good moisture-proof and thermotolerance, but initial polarization property is generally not enough as the polarizer comprising dye of the polarizer.
And in by the middle tone polarization plates that several two look dyestuffs absorption in the polymer film and orientation is prepared, when the specific wavelength of visible region particularly the 400-700nm wavelength region may make its state oriented perpendicular to each other (crossing condition) issue the third contact of a total solar or lunar eclipse when leaking (color leakage) piling up two polarization plates, the tone of LCD changes sometimes under dark state when this polarization plates is connected on the liquid crystal panel.Based on this, in order to prevent when polarization plates is connected on the liquid crystal indicator under dark state owing to the color to specific wavelength leaks the variable color that produces LCD, the penetrability under the crossing condition (crossing condition penetrability) must be in the visible region particularly the 400-700nm wavelength region may evenly reduce.
In addition, be under the situation of color liquid crystal projector at the color liquid crystal projection type display, polarization plates is to be used for the part that liquid crystal image forms.But because light is polarized plate and obviously absorbs, and the small size image of 0.9-6 inch is amplified to about tens times to 100 times, and its brightness reduces inevitably, makes the light source that must use high brightness.And the brightness of liquid crystal projection apparatus more needs further increase, and the intensity of the used light source of result is increasing.
Therefore, the general polarization plates that forms the zone with middle gray scale iodine type polarization plates as the liquid crystal image of color liquid crystal projector with satisfied polarization property.But because the polarizer is an iodine, there is the problem of fastness to light, thermotolerance and humidity resistance deficiency in iodine type polarization plates.In order to address this problem, used with the middle gray scale polarization plates of dye-type two look colorants as the polarizer.In this, in the gray scale polarization plates, be used in combination with penetrability and polarization property in the whole visible wavelength range of average improvement (400-700nm) with three look dyestuffs.Therefore, with respect to the market demands of color liquid crystal projector high brightness, its penetrability is too poor, and has the display device of problem to obtain becoming clear that must improve the intensity of light source.In order to address this problem, having brought into use is respectively three kinds of polarization plates of blue channel, green channel and red channel with respect to three primary colors.
As the dyestuff that is used to make polarization plates, for example, day disclosure special permission communique No.2844360 discloses the water-soluble dye of a kind of following general formula (7) in embodiment 1.
But the polarization plates that contains above-mentioned water-soluble dye is at the needs that can not satisfy the user aspect polarization property, absorbing wavelength zone and the tone fully.
In addition, be in three kinds of polarization plates of blue channel, green channel and red channel at three primary colors with respect to the color liquid crystal projector, the polarization plates that is used for green channel (green glow) lacks good brightness and polarization property, need make improvements.
An object of the present invention is to provide a kind of have good polarization property, water proofing property and stable on heating high performance polarization plates.And, another object of the present invention provides a kind of by two kinds or multiple two look dyestuffs adsorbs in polymer film and the directed high performance middle tone polarization plates that forms, its under crossing condition in the visible region particularly the 400-700nm wavelength region may color does not take place leaks, and have good polarization property, water proofing property and thermotolerance.
Further purpose of the present invention provides a kind of polarization plates that is used for green channel (green glow) in the trichromatic three kinds of polarization plates with respect to the color liquid crystal projector and has the high-performance polarization plates of good brightness and polarization property.
Disclosure of an invention
In order to achieve the above object, the inventor has carried out deep research, and find that the polarizing coating and the polarization plates that contain a kind of particular dye have good polarization property, water proofing property and thermotolerance, and further find, dyestuff by adding a kind of special selection is to provide the polarization plates with middle tone and above-mentioned particular dye, the polarization plates that can obtain having good polarization property and permanance and not have color to leak in the visible region, also further find by adding a kind of two special look dyestuffs separately or with the dyestuff of other selection, what can obtain being applicable to green channel (green glow) has good brightness and polarization property polarizing coating and a polarization plates, thereby has finished the present invention.
Therefore, the present invention relates to:
1, a kind of polyvinyl alcohol (PVA) type polarizing coating, contain water-soluble dye or its copper complex salt dyestuff by following general formula (1) expression of free sour form at the substrate that is used for this polarizing coating:
[wherein A represents following general formula (2)
Figure A0081009600082
B represents following general formula (4) when A represents general formula (2);
Figure A0081009600083
And n is 1, the R in the general formula (4) 5Expression amino or hydroxyl, perhaps
A represents following general formula (3)
Figure A0081009600084
{ wherein X represents nitro or amino }, B represents following general formula (5) when A represents general formula (3);
Figure A0081009600085
And n be 0 or 1{ general formula (5) in R 6Expression hydrogen atom, hydroxyl, replacement or unsubstituted amino, methyl, ethyl, methoxy or ethoxy, R 7Expression hydrogen atom, hydroxyl, replacement or unsubstituted amino, methyl, ethyl, methoxy or ethoxy }, R 1, R 2, R 3, R 4Represent hydrogen atom, methyl, ethyl, methoxyl, ethoxy and acetylamino independently of one another, its precondition be when n be 1, when A represents that general formula (2) and B represent general formula (4), get rid of all R 1, R 2, R 3And R 4All be the situation and the R of methyl or methoxy 1And R 3Be methyl and R 2And R 4Situation for methoxyl].
2, a kind of as above-mentioned the 1st defined polyvinyl alcohol (PVA) type polarizing coating, this polarizing coating contain at least a water-soluble dye or its copper complex salt and at least a organic dyestuff that is different from above-mentioned dyestuff by general formula (1) expression.
3, a kind of polyvinyl alcohol (PVA) type polarization plates contains a kind of diaphragm on the surface of any defined polyvinyl alcohol (PVA) type polarizing coating of this polarization plates in as the above-mentioned the 1st and the 2nd.
4, a kind of polyvinyl alcohol (PVA) polarizing coating that is used for the green channel of liquid crystal projection apparatus, the substrate that is used for polarizing coating contain free sour form by the water-soluble dye of following general formula (6) expression and have more than or equal to 520nm and less than the maximum absorption wavelength (λ max) of 580nm:
Figure A0081009600091
(R wherein 8, R 9, R 10And R 11Represent hydrogen atom, methyl, ethyl, methoxyl, ethoxy and acetylamino independently of one another, R 12Expression hydrogen atom, amino or hydroxyl).
5, a kind of polyvinyl alcohol (PVA) polarizing coating that is used for the green channel of liquid crystal projection apparatus, this polarizing coating contain at least a water-soluble dye and at least a organic dyestuff that is different from above-mentioned dyestuff by defined general formula (6) expression in above-mentioned the 4th.
6, a kind of as the above-mentioned the 4th or the 5th defined polyvinyl alcohol (PVA) type polarization plates that is used for the green channel of liquid crystal projection apparatus, wherein the average penetrability of the crossing condition when 630-780nm is more than or equal to 60%.
7, a kind of polyvinyl alcohol (PVA) type polarization plates that is used for the green channel of liquid crystal projection apparatus contains a kind of diaphragm on the surface of this polarization plates defined polyvinyl alcohol (PVA) type polarizing coating in as above-mentioned the 4th.
8, a kind of color liquid crystal projector, this projector is defined polarization plates in green channel partly contains as above-mentioned the 7th.
Contain one or more and have good polarization property and good water proofing property and thermotolerance by the water-soluble dye of general formula (1) expression or the polarization plates of its copper complex salt dyestuff.And it is all very good and have a neutral tone (gray scale) to contain one or more its polarization property of polarization plates, water proofing property and thermotolerances by the water-soluble dye of general formula (1) expression or its copper complex salt dyestuff and one or more other organic dyestuff.
In addition, be used to have and contain one or more by the water-soluble dye of general formula (6) expression and have more than or equal to 520nm and less than the polarization plates of the liquid crystal projection apparatus of the polarizing coating of the maximum absorption wavelength (λ max) of 580nm and as the polarization plates of green channel (green glow) time, have good brightness and polarization property.Implement best way of the present invention
At first explanation is used for water-soluble dye or its copper complex salt dyestuff by general formula (1) expression of polarizing coating of the present invention.
Water-soluble dye or its copper complex salt dyestuff by general formula (1) expression that are used for polarizing coating of the present invention comprise two groups of dyestuffs, one group is that wherein A represents that general formula (2), B represent that general formula (4) and n are 1 dyestuff, one group is that A represents that general formula (3), B represent that general formula (5) and n are 0 or 1 dyestuff, and every group of dyestuff can be the form of free acid and salt.
Described salt can comprise, for example, alkali metal salt such as sodium salt, sylvite and lithium salts, ammonium salt, ethanolamine salt and alkylamine salt, sodium salt generally are preferred.
In addition in the present invention, contain polarizing coating by the water-soluble dye of general formula (1) expression or its copper complex salt dyestuff and be meant generally polarizing coating by the polarizing coating substrate being dyeed with above-mentioned dyestuff and its stretching, extension being obtained, dyestuff wherein may reside in the surface of film substrate or the inside of film, and these two kinds of situations all comprise in the present invention.
In the used water-soluble dye by general formula (1) expression of the present invention, A represents that general formula (2), B represent that general formula (4) and n are in 1 the dye set therein, and the position of substitution of the sulfo group in the general formula (2) is preferably in the contraposition of azo group.R 1, R 2, R 3And R 4Represent hydrogen atom, methyl, ethyl, methoxyl, ethoxy or acetylamino independently of one another, preferably R wherein 1And R 2Represent hydrogen atom, methyl, methoxyl or acetylamino separately and R 3And R 4The compound of representing methyl, ethyl or methoxyl independently of one another.R more preferably 1And R 2It all is the compound of hydrogen atom.Preferred in the case compound can comprise R 3And R 4All be the compound of methyl or ethyl, most preferably R 3And R 4It all is the compound of methyl.R in the general formula (4) 5Expression amino or hydroxyl, preferred amino.R 5The position of substitution particularly preferably be contraposition at-NHCO-base.Wherein A represents that general formula (2), B represent that general formula (4) and n are that the exemplary of 1 dye set is listed in down with the form of free acid:
Figure A0081009600111
In addition, in the used water-soluble dye by general formula (1) expression of the present invention, A represents that general formula (3), B represent that general formula (5) and n are that the X in the general formula (3) represents nitro or amino, preferably nitro in 0 or 1 the dye set therein.R 1, R 2, R 3And R 4Represent hydrogen atom, methyl, ethyl, methoxyl, ethoxy or acetylamino independently of one another, preferably R wherein 1And R 2Represent methyl, methoxyl or acetylamino separately and n is 0 compound, more preferably R wherein 1Be methyl or methoxy and R 2Compound for methoxyl.Particularly preferably be wherein R 1And R 2It all is the compound of methoxyl.R in the general formula (5) 6Expression hydrogen atom, hydroxyl, replacement or unsubstituted amino, methyl, ethyl, methoxy or ethoxy, preferably hydroxyl.R in the general formula (5) 7Expression hydrogen atom, hydroxyl, replacement or unsubstituted amino, methyl, ethyl, methoxy or ethoxy, preferably hydrogen atom, hydroxyl or carbamyl, more preferably hydrogen atom or hydroxyl.R 6And R 7In the amino of replacement can comprise that for example, low-carbon alkyl is amino as methylamino, carbamyl amino or low-carbon (LC) acyl amino such as acetylamino.R 7The position of substitution preferably at the ortho position of azo group.
In the present invention, term " low-carbon (LC) " is meant to have 1-5 carbon atom, more preferably 1-3 carbon atom.
In the used water-soluble dye by general formula (1) expression of the present invention, wherein A represents that general formula (3), B represent that general formula (5) and n are that the exemplary of 0 or 1 dye set is listed in down with free sour form:
Figure A0081009600121
Figure A0081009600131
The water-soluble dye that is used for according in the green channel polarization plates of liquid crystal projection apparatus of the present invention is described below.
The water-soluble dye of green channel that is used for the present invention's liquid crystal projection apparatus is as two look molecules, this water-soluble dye can comprise the water-soluble dye by general formula (6) expression, can use and anyly have more than or equal to 520nm and less than the water-soluble dye of the maximum absorption wavelength (λ max) of 580nm, these dyestuffs can be the forms of free acid, also can be the forms of salt.Described salt can comprise, for example, and alkali metal salt such as sodium salt, sylvite and lithium salts, ammonium salt, ethanolamine salt and alkylamine salt, preferably sodium salt.
Water-soluble dye by general formula (6) expression is 1 corresponding to its formula of (2) expression A, general formula (4) expression B and n, and have more than or equal to 520nm and less than the dyestuff of the general formula (1) of the maximum absorption wavelength (λ max) of 580nm, wherein can continue to use the description of mutual-through type (6) compound and mutual-through type (1) is described.
The exemplary that is used for the water-soluble dye by general formula (6) expression of the present invention is listed in down with the form of free acid:
Figure A0081009600141
The water-soluble dye among the present invention of being useful on by general formula (1) expression, its copper complex salt dyestuff or can be according to the general production technology of azo dyes by the water-soluble dye of general formula (6) expression is by carrying out known diazotising, coupling or optionally carrying out the formation of copper complex salt and preparation simply.Concrete preparation method comprise A in its formula of (1) represent general formula (2), B represent general formula (4) and n be 1 dye set and wherein A represent that general formula (3), B represent that general formula (5) and n are two kinds of methods of 0 or 1 dye set.Be described in more detail below these methods.
(I) A represents that general formula (2), B represent that general formula (4) and n are the production method of 1 dye set in the general formula (1):
The aniline diazotising that will replace with the sulfonic group of general formula (2) and can have substituent aniline and carries out the one-level coupling, obtains the monoazo amino-compound.Then with this monoazo amino-compound diazotising and with can have substituent aniline and carry out the secondary coupling, obtain two azo amino-compounds.With this two azos amino-compound diazotising; and with naphthols corresponding to target compound; promptly wherein the phenyl of benzoyl nuclear is carried out three grades of couplings by the N-benzoyl J acid of amino or hydroxyl replacement at the aniline state, obtains the water-soluble dye by general formula (1) expression.In addition, when forming the copper complex salt with copper sulphate etc., obtain copper complex salt by the water-soluble dye of general formula (1) expression with conventional method.
Wherein A represents that general formula (2), B represent that general formula (4) and n are that the initiation material of 1 dye set is the aniline that sulfonic group replaces, and this aniline can comprise, for example, and sulfanilic acid, metanilic acid and orthanilic acid.
Can comprise methyl, ethyl, methoxyl, ethoxy and acetylamino as the component of firsts and seconds coupling and the substituting group that can have substituent aniline.On the phenyl of this aniline, can there be one or two these substituting groups.Be 2-position or 3-position with respect to the bonding position of amino under the substituent situation having, be preferably 2-position and 5-position under two substituent situations having.This can have substituent aniline and can comprise, for example, aniline, 2-aminotoluene, 3-methylaniline, 2-ethylaniline, 3-ethylaniline, 2,5-xylidin, 2,5-diethylaniline, 2-aminoanisole, 3-aminoanisole, 2-methoxyl-5-methylaniline, 2,5-dimethoxyaniline and 2-methoxyl-5-acetylaminoaniline.The amino of aniline can be protected.
Protecting group can comprise, for example, and its ω-Loprazolam base.The aniline that is used for the one-level coupling can be same to each other or different to each other with the aniline that is used for the secondary coupling.
Wherein benzoyl can be comprised by the N-benzoyl J acid of the naphthols of three grades of coupling components of conduct of amino or hydroxyl replacement; N-(4 '-amino benzoyl) J acid; N-(2 '-amino benzoyl) J acid, N-(4 '-hydroxy benzoyl) J acid and N-(2 '-hydroxy benzoyl) J acid.
The N-benzoyl J acid that is replaced by an amino or hydroxyl for benzoyl wherein, wherein R 5For the compound of amino can obtain nitration product then by using the chlorobenzoyl chloride that is replaced by nitro to carry out benzoylation according to known method this J acid according to the known method reduction.In addition, R wherein 5For the N-benzoyl J acid of hydroxyl also can form by known method.
In addition, also can be by the water-soluble dye of general formula (6) expression according to the general production technology of azo dyes in the mode identical with above-mentioned production technology, the preparation simply by carrying out known diazotising and coupling method obtains the water-soluble dye of general formula (6).
(II) wherein A represents that general formula (3), B represent that general formula (5) and n are the production method of 0 or 1 dye set:
With X in the general formula (3) be nitro 4-nitro-4 '-aminobenzene vinyl benzene-2,2 '-sodium disulfonate carries out diazotising, and with can have substituent aniline and carry out the one-level coupling, obtain the monoazo amino-compound.Then with this monoazo amino-compound diazotising and with can have substituent aniline and carry out the secondary coupling, obtain two azo amino-compounds.With this two azos amino-compound diazotising, and under the aniline state, carry out three grades of couplings, obtain n and be 1 water-soluble dye by general formula (1) expression with the naphthols that is replaced by azo group by general formula (5) expression.It for n 0 water-soluble dye, when the diazotising product of monoazo amino-compound carries out the secondary coupling with the naphthols that is replaced by the azo group by general formula (5) expression under the aniline state, can obtain wherein n and be 0 and X be the water-soluble dye by general formula (1) expression of nitro.
Wherein X obtains for the amino water-soluble dye by general formula (1) expression can be converted into amino by the nitro that the above-mentioned X by general formula (1) expression that obtains is the water-soluble dye of nitro.Can be by with reduction such as sodium sulphide and nitro is converted into amino.
In addition, can form the copper complex salt with copper sulphate etc. from the above-mentioned water-soluble dye that obtains with conventional method, and obtain copper complex salt (copper complex salt dyestuff) by the water-soluble dye of general formula (1) expression.
Represent at A under the situation of general formula (3) initiation material be generally 4-nitro-4 '-aminobenzene vinyl benzene-2,2 '-sodium disulfonate.
Can comprise methyl, ethyl, methoxyl, ethoxy and acetylamino as the component of one-level or secondary coupling and the substituting group that can have substituent aniline.On the phenyl of this aniline, can there be 1 or 2 this substituting group.Be 2-position or 3-position with respect to the coupling position of amino under the substituent situation having, be preferably 2-position and 5-position under two substituent situations having.This can have substituent aniline and can comprise, for example, aniline, 2-aminotoluene, 3-methylaniline, 2-ethylaniline, 3-ethylaniline, 2,5-xylidin, 2,5-diethylaniline, 2-aminoanisole, 3-aminoanisole, 2-methoxyl-5-methylaniline, 2,5-dimethoxyaniline and 2-methoxyl-5-acetylaminoaniline.The amino of aniline can be protected.
Protecting group can comprise, for example, and its ω-Loprazolam base.The aniline that is used for the one-level coupling can be same to each other or different to each other with the aniline that is used for the secondary coupling.
The naphthols that the azo group by general formula (5) expression that uses in the last coupling step in said method replaces can comprise, for example, 6-(4 '-the hydroxy phenyl azo group)-3-sulfonic acid-1-naphthols, 6-(2 ', 4 '-the dihydroxy phenyl azo group)-3-sulfonic acid-1-naphthols, 6-(2 '-acetylaminohydroxyphenylarsonic acid 4 '-the hydroxy phenyl azo group)-3-sulfonic acid-1-naphthols, 6-(4 '-aminophenyl azo group)-3-sulfonic acid-1-naphthols and 6-(4 '-N-methylamino phenyl azo group)-3-sulfonic acid-1-naphthols.The naphthols that is replaced by azo group by general formula (5) expression can by according to known method with J acid tosylation and diazotising, then it is carried out the piptonychia benzene sulfonylization and obtains with phenol and aniline coupling.In addition, wherein A represents that general formula (3), B represent that general formula (5) and n are that 0 or 1 dye set can be by being carried out coupling with the J acid substitution by the naphthols that the azo group by general formula (5) expression replaces, and then the amino of J acid is converted into the azo group of general formula (5) according to conventional method and forms.That is to say it can by with the amino diazotising of the J acid of coupling and with by having R 6And R 7The substituent phenylol of expression or aniline carry out coupling and obtain.
In aforementioned production method, diazotation step is undertaken by the conventional method that nitrite such as sodium nitrite are mixed in mineral acid example hydrochloric acid or sulfuric acid in the aqueous solution of diazo reagent or suspending liquid, perhaps by carrying out in the neutral or weakly alkaline aqueous solution that nitrite is joined diazo reagent and with its inverse approach that mixes with mineral acid.Diazotizing temperature is approximately-10 to 40 ℃.In addition, under the acid condition of pH 2-7, mix at-10 ℃ to 40 ℃ with above-mentioned diazonium solution by acidic aqueous solution with the coupling step of aniline and carry out hydrochloric acid or acetate.
The Monoazo compound that obtains by coupling and two azo-compounds can its separate by acid saltout when forming precipitation or precipitation after separate by filtration and to enter next step then, perhaps the form with its original solution or suspending liquid enters next step.Be indissoluble and be under the situation of form of suspension at diazo salt, can filter and obtain filter press cake, use it for then in the diazotation step subsequently.
The diazonium product of Monoazo compound or two azo-compounds and and under the alkali condition of-10 ℃ to 40 ℃ temperature and pH 7-10, carrying out by the secondary between the naphthols of the group coupling of general formula (4) or general formula (5) expression or three grades of coupling reactions.After reaction was finished, product was by saltouing precipitated and passing through filtered and recycled.In addition, in order to form the copper complex salt, its aqueous solution and copper sulphate or cupric chloride are existed, for example, ammonia, monoethanolamine or diethanolamine exist down 95-100 ℃ of reaction, and precipitate by saltouing and pass through filtered and recycled.If necessary purifying can repeat to saltout and maybe product can be precipitated from water with organic solvent.
This organic solvent can comprise water-miscible organic solvent, for example, and alcohols such as methyl alcohol and ethanol and ketone such as acetone.
In addition, for polarizing coating of the present invention or polarization plates, can use separately by the water-soluble dye of general formula (1) expression or its copper complex salt dyestuff or by the water-soluble dye of general formula (6) expression, perhaps can optionally be used in combination with one or more other organic dyestuff.Used organic dyestuff is had no particular limits, and preferably those wavelength coverages in the wavelength region may that is different from water-soluble dye of the present invention or its copper complex salt have the feature of absorption and have high dichromatic dyestuff.They comprise, for example, C.I. direct yellow 12, C.I. direct Huang 28, C.I. Direct Yellow 44, C.I. direct orange 26, C.I. direct orange 39, C.I. direct orange 107, and C.I. is directly red 2, and C.I. directly red 31, C.I. directly red 79, C.I. directly red 81, C.I. is directly red 247, C.I. direct green 80, C.I. direct green 59, and at day disclosure special permission communique 145255/1984, day disclosure special permission communique 156759/1985, those dyestuffs of describing in day disclosure special permission communique 12606/1991 and day disclosure special permission communique 218610/1999 publication such as grade.This dyestuff uses with the form of free acid or alkali metal salt, ammonium salt or amine salt.
When other organic dyestuff optionally uses together, the ratio of mixing has no particular limits, but other organic dyestuff is generally preferably being that benchmark is aggregated in the scope of common 0.1-10 part and uses by the water-soluble dye of general formula (1) expression or its copper complex salt or by the quality of the water-soluble dye of general formula (6) expression.
For polarizing coating of the present invention or the polarizing coating that is used for the green channel polarization plates of liquid crystal projection apparatus of the present invention, the polarizing coating of various color harmony neutralc tints can prepare by adding water-soluble dye or its copper complex salt of being represented by general formula (1) according to known method or also optionally add other organic dyestuff together by the water-soluble dye that general formula (6) is represented in polymer film.For providing diaphragm, the gained polarizing coating obtains polarization plates; protective seam or AR layer and stilt also optionally are provided; it can be used for liquid crystal projection apparatus; desk-top calculator, wrist-watch, notebook personal computer; word processor; the LCD TV device, automobile navigation instrument, instrument or display that indoor or outdoors uses.
The substrate (polymer film) that is used for polarizing coating of the present invention is preferably polyvinyl alcohol (PVA) type substrate, this polyvinyl alcohol (PVA) type substrate can comprise, for example, the polyvinyl alcohol or derivatives thereof, and they one of with the modified product of alkene such as ethene or propylene or unsaturated carboxylic acid such as crotonic acid, acrylic acid, methacrylic acid or maleic acid.In the middle of them, consider that from the absorbability and the directionality of dyestuff the film that contains the polyvinyl alcohol or derivatives thereof is more suitable.
When water-soluble dye, or, adopt method usually with polymer film dyeing by its copper complex salt dyestuff of general formula (1) expression with when joining in the above-mentioned polymer film by the water-soluble dye of general formula (6) expression with general formula (1) expression.Dyeing for example, is carried out according to following method.At first water-soluble dye is dissolved in and prepares dye bath in the water.Concentration to dyestuff in the dye bath has no particular limits, and is typically chosen in the scope of about 0.001-10 weight %.Can optionally use dyeing assistant.For example, the sodium sulphate that can working concentration be approximately 0.1-10 weight %.Polymer film is immersed in the prepared dye bath dyes.Dyeing temperature is preferably about 40-80 ℃.
The polymer film that is colored stretches with to water-soluble dye (two chromatic colorant agent) orientation.Can use any known stretching method, for example wet method and dry method.Polymer film can according to circumstances stretch before dyeing.In the case, water-soluble dye carries out orientation by dyeing.The polymer film of adding water-soluble dye and orientation optionally carries out aftertreatment with known method such as boric acid is handled.Adopt this aftertreatment can improve the penetrability and the degree of polarization of polarizing coating.The condition that boric acid is handled is according to the kind of the kind of used polymer film and used dyestuff and different.The concentration of boric acid aqueous solution mesoboric acid is generally at 0.1-15 weight %, and in the scope of preferred 1-10 weight %, treatment temperature is 30-80 ℃, preferred 40-75 ℃.In addition, can in containing the aqueous solution of cationic polymer, fix processing as required together.
Can in the one side of gained dye type polarizing film or two stickups, have the diaphragm of good light transmission and physical strength to form polarization plates.The material that forms diaphragm can be existing those materials.Described film comprises, for example, cellulose acetate type film or acrylic film, and fluorine type film such as tetrafluoroethylene/hexafluoropropylene copolymer contain the film of vibrin, polyolefin resin or polyamide.
A kind of protective clear layer can be further contained on the surface of polarization plates of the present invention.This protective seam can comprise, for example, and acrylic acid or polysiloxane type hard conating or urethane type protective seam.In order to improve the veneer penetrability, preferably on protective seam, arrange AR (anti-reflecting layer) in addition.The AR layer can pass through, and for example, the vapour deposition of material such as silicon dioxide or titanium dioxide or splash and form perhaps also can form by the scumbling fluorine-containing material.Be also included within the polarization plates of the present invention by augment the oval polarization plates that phase difference plate forms to polarization plates.
The characteristics of the polarization plates of Gou Chenging are to have neutralc tint like this, under crossing condition in the visible region particularly the 400-700nm wavelength region may do not produce color and leak, have good polarization property, do not produce variable color or reduce polarization property and seldom light leakage under crossing condition in the visible region at humid tropical condition.
The polarization plates of the present invention that is used for the green channel of liquid crystal projection apparatus have contain as two look molecules by the water-soluble dye of general formula (6) expression and have more than or equal to 520nm and less than the maximum absorption wavelength (λ max) of 580nm and optionally contain the polarizing coating of above-mentioned other organic dyestuff.In addition; the polarizing coating of the present invention of polarization plates that is used for the green channel of liquid crystal projection apparatus also is to prepare according to the method described in the preparation method of polarizing coating of the present invention by recited above; and further provide diaphragm to form polarization plates; and protective seam or AR layer and stilt optionally are provided, with the polarization plates of the green channel that acts on liquid crystal projection apparatus.
Maximum absorption wavelength (λ max) is meant the maximum absorption wavelength under two polarization plates oriented stack state intersected with each other of using the two look dyeings of being represented by general formula (6).
In order to be used for the green channel of liquid crystal projection apparatus, polarization plates preferably has more than or equal to the average penetrability of 39% veneer with smaller or equal to the average penetrability of crossing condition under 0.4% the 500-580nm and more than or equal to the average penetrability of crossing condition under 60% the 630-780nm, more preferably, polarization plates has more than or equal to the average penetrability of 41% veneer with smaller or equal to the average penetrability of crossing condition under the 500-580nm of 0.3% (be more preferably less than and equal 0.2%) and more than or equal to the average penetrability of crossing condition under 70% the 630-780nm.Further preferably, polarization plates has more than or equal to the average penetrability of 42% veneer with smaller or equal to the average penetrability of crossing condition under 0.1% the 500-580nm and more than or equal to the average penetrability of crossing condition under 80% the 630-780nm.Above-mentioned polarization plates shows red under neutral light, is called colored polarization plates.The colored polarization plates that is used for green channel of the present invention has good brightness and polarization property as previously mentioned.
The polarization plates that is used for liquid crystal projection apparatus of the present invention can further provide the AR layer to make the polarization plates that has the AR layer by giving the polarization plates that contains polarizing coating and protective seam.In addition, provide support thing such as transparency glass plate to make the polarization plates that has stilt can for the polarization plates contain the polarization plates of polarizing coating and protective seam or to have an AR layer.
The average penetrability of veneer be meant be not with the AR layer and do not have stilt such as the polarization plates of transparency glass plate (abbreviate polarization plates as, in the description of back, also have identical meaning) under neutral light incident at the mean value of the penetrability of particular range of wavelengths.Average penetrability under the crossing condition is meant two polarization plates that align intersected with each other mean value in the penetrability of particular range of wavelengths under neutral light incident.
The polarization plates that is used for liquid crystal projection apparatus of the present invention preferably has the polarization plates of stilt, and polarization plates wherein sticks on stilt such as the transparency glass plate.Further preferably have the polarization plates of AR layer and stilt, the polarization plates that wherein has the AR layer sticks on the stilt.
The general polarization plates that has stilt of using of polarization plates that is used for liquid crystal projection apparatus of the present invention.Stilt preferably has planar section and is used to paste polarization plates, is preferably glass moldings, because it is to be used for optical applications.Glass moldings can comprise, for example, and glass plate, camera lens, prism (triangular prism, block prism).The camera lens that has polarization plates can be as the condenser that has polarization plates in the liquid crystal projection apparatus.In addition, the prism that has a polarization plates can or have two prisms of polarization plates as the polarisation beam shunt that has polarization plates in the liquid crystal projection apparatus.And it can append in the liquid crystal cells.The material of glass can comprise, for example, and inorganic type glass such as sodium carbonate glass, borosilicate glass or sapphire glass, and organic glass such as acrylic acid or polycarbonate type glass.Inorganic type glass preferably.The thickness of glass plate and size can have desirable yardstick.For the polarization plates that has glass, preferably worn the AR layer in addition, with the further veneer penetrability of improving in the one side or two on glass surface or polarization plates surface.
The polarization plates that has stilt that is used for liquid crystal projection apparatus can be passed through, and for example, clear binder is coated to the planar section of stilt, coated side is bonded on the polarization plates of the present invention to prepare then.Perhaps also clear binder can be coated on the polarization plates stilt is bonded on its coated side.Bonding agent used herein is preferably acrylic ester type.In addition, when oval polarization plates when the polarization plates, the surface with the plate of the phase difference plate side bonds on the stilt usually, and the side of polarization plates bonds on the glass moldings.
In the color liquid crystal projector that uses polarization plates of the present invention, polarization plates, the more preferably above-mentioned colored polarization plates that has stilt is disposed in the green channel part.The polarization plates of the light source plane of incidence is exposed under the high light.Thereby temperature raises.Polarization plates on liquid crystal cells and the light source plane of incidence is when common liquid crystal display cells closely contacts each other, the heat transferred of the polarization plates on the light source plane of incidence is to liquid crystal cells, the temperature of the liquid crystal in the liquid crystal cells surpasses NI point (phase transition temperature, nematic-isotropy type transformation temperature) and can not show.For fear of this problem, the polarization plates on the liquid crystal cells and the light source plane of incidence is separated, and make air or gas communication, to prevent liquid crystal cells overheated (can be water-cooling system) by air-cooler etc.
That is to say that in using the colour liquid crystal display device of polarization plates of the present invention, polarization plates of the present invention is positioned in the plane of incidence of liquid crystal cells of green channel and the one side in the surface of emission or two.Polarization plates can or not contact with liquid crystal cells, but considers that permanance does not preferably contact with liquid crystal cells.Use behind in the system of PBS (polarisation beam shunt) at light source, can use iodine type polarization plates, perhaps can be with polarization plates of the present invention as the polarization plates on the plane of incidence., under situation about contacting on the surface of emission, can use to have of the present invention polarization plates of liquid crystal cells at polarization plates and liquid crystal cells as stilt.Polarization plates not with situation that liquid crystal cells contacts under, the preferred polarization plates of the present invention that adopts the stilt beyond the liquid crystal cells of using.Consider permanance in addition, preferably all settle polarization plates of the present invention at the plane of incidence and the surface of emission two faces of liquid crystal cells, more preferably the surface with polarization plates of the present invention is placed in the liquid crystal cells one side, and the surface of stilt is placed in the light source one side.The plane of incidence of liquid crystal cells is meant the one side towards light source, and its reverse side is called the surface of emission.
In using the color liquid crystal projector of polarization plates of the present invention, preferably filter is cut in the arrangement ultraviolet ray between light source and the polarization plates that has stilt at the plane of incidence.In addition, used liquid crystal cells is, for example, active matrix type, and preferably by with sealing liquid crystal and the transparent base that forms of electrode and TFT and and the transparent base that forms of counter electrode between make.Cut filter and be divided into three primary colors by ultraviolet ray from the light of light source such as the emission of metal halide bulb, green light is used for green channel of the present invention by having the colored polarization plates of stilt then, combines with other two look then, amplify by projection lens, project on the screen then.
The polarization plates of the green channel that is used for the color liquid crystal projector of Gou Chenging can be used as the colored polarization plates of green channel like this, have good brightness and polarization property, the average penetrability of its veneer is more than or equal to 41%, and the average penetrability in the 500-580nm absorbing wavelength scope under the crossing condition is smaller or equal to 0.2.
Embodiment
The present invention will carry out more specific description by the following examples, but these embodiment only are used for explanation, but not limitation of the invention.Except as otherwise noted, % among each embodiment and umber all are benchmark with the quality.Synthesis example 1, compound 1 and 16 synthetic.
(a) with 29.9 parts of 4-aminoazabenzols-4 '-sodium sulfonate joins in 600 parts of water and 70 ℃ of dissolvings down.It is cooled to below 30 ℃, adds 32 part 35% hydrochloric acid, add 6.9 parts of sodium nitrites then, stirred 2 hours at 25-28 ℃.Adding 12.1 part 2, the 5-xylidin and 25-30 ℃ stir 2 hours after,, and continue to stir with pH regulator to 3 with sodium carbonate to finish coupling reaction, filter and obtain two azo-compounds.After being dispersed in gained two azo-compounds in 600 parts of water, add 32 part 35% hydrochloric acid, add 6.9 parts of sodium nitrites then, stir at 25-30 ℃ and carried out diazotising in 2 hours.
In addition, 35.8 parts of N-(4 '-amino benzoyl) J acid is joined in 250 parts of water, make it be alkalescent and dissolving with sodium carbonate.The diazotising product of front gained two azo-compounds is poured in this solution, kept neutral simultaneously, stir to finish coupling reaction to weak basic condition.Product is saltoutd with sodium chloride and filter, obtain the water-soluble dye (sodium salt) of the trisazo compound of compound 1.
(b) by with 2,5-diethylaniline replacement 2, the 5-xylidin obtains the water-soluble dye (sodium salt) of compound 16.Synthesis example 2, compound 2 synthetic.
Join 17.3 parts of sulfanilic acid in 500 parts of water and use dissolution of sodium hydroxide.It is cooled to below 10 ℃, adds 32 part 35% hydrochloric acid, add 6.9 parts of sodium nitrites then, stirred 1 hour at 5-10 ℃.Adding 13.7 parts, to be dissolved in paracresol in the watery hydrochloric acid fixed and 10-15 ℃ of stirring, by adding sodium carbonate with pH regulator to 3, and continues to stir to finish coupling reaction, filters and obtain Monoazo compound.After being dispersed in the gained Monoazo compound in 600 parts of water, add 32 part 35% hydrochloric acid, add 6.9 parts of sodium nitrites then, stirred 2 hours at 25-30 ℃.Add 15.3 parts and be dissolved in 2 in the watery hydrochloric acid, 5-dimethoxyaniline and 20-30 ℃ of stirring by adding sodium carbonate with pH regulator to 3, and continues to stir to finish coupling reaction, filters and obtains two azo-compounds.After being dispersed in gained two azo-compounds in 600 parts of water, add 32 part 35% hydrochloric acid, add 6.9 parts of sodium nitrites then, stir at 25-30 ℃ and carried out diazotising in 2 hours.
In addition, join in 250 parts of water 35.8 parts of N-(4 '-amino benzoyl) J acid and dissolving, make it be alkalescent with sodium carbonate simultaneously.The diazotising product of front gained two azo-compounds is poured in this solution, kept neutral simultaneously, stir to finish coupling reaction to weak basic condition.Product is saltoutd with sodium chloride and filter, obtain the water-soluble dye (sodium salt) of the trisazo compound of compound 2.Synthesis example 3, compound 3 synthetic.
The compound that obtains in 40 parts of synthesis examples 2 is dispersed in 500 parts of water, adds 15 parts of crystal copper sulphate and 15 parts of monoethanolamines, be heated to 95 ℃ and reacted 10 hours.Make reactant liquor saltout and filter by adding sodium chloride, obtain the copper complex salt dyestuff (sodium salt) of compound 3.Synthesis example 4, compound 6 synthetic.
With 44.4 parts of 4-nitros-4 '-aminobenzene vinyl benzene-2,2 '-sodium disulfonate joins in 600 parts of water and 70 ℃ of dissolvings down.It is cooled to below 30 ℃, adds 32 part 35% hydrochloric acid, add 6.9 parts of sodium nitrites then, stirred 2 hours at 25-30 ℃.Adding 15.3 part 2, the 5-dimethoxyaniline and 25-30 ℃ stir 2 hours after, by adding sodium carbonate, and continue to stir to finish coupling reaction with pH regulator to 3, filter and obtain Monoazo compound.After being dispersed in the gained Monoazo compound in 600 parts of water, add 32 part 35% hydrochloric acid, add 6.9 parts of sodium nitrites then, stir at 25-30 ℃ and carried out diazotising in 2 hours, obtain the diazo-reaction solution of monoazo.
In addition, 24.0 parts of J acid are dispersed in 250 parts of water, make its dissolving, add 19 parts of toluene sulfochlorides, stirred 1 hour at 35-40 ℃ by adding 12 parts of NaOH.The hydrochloric acid that adds 42 part 35% in this solution adds 6.9 parts of sodium nitrites then, stirs 2 hours at 10-15 ℃.After adding 9.4 parts of phenol, add NaOH with pH regulator to 9, with its 10-15 ℃ of stirring to finish coupling reaction.In reaction solution, add 6 parts of NaOH, stir at 80 ℃ and made its hydrolysis in 3 hours.After being cooled to 20-30 ℃, add 35% hydrochloric acid with pH regulator to 7, saltout and filter by adding sodium chloride then, obtain Monoazo compound 6-(4 '-hydroxy phenyl azo)-3-sulfonic acid-1-naphthols.This Monoazo compound is joined in 300 parts of water, make its dissolving by adding NaOH.
The diazo-reaction solution of the monoazo that obtains is previously joined in the described solution that is dissolved with Monoazo compound, keeps weak basic condition with sodium carbonate simultaneously, 15-25 ℃ of stirring to finish coupling reaction.This reaction solution by adding sodium chloride and saltout and filtering, is obtained the water-soluble dye (sodium salt) of the trisazo compound of compound 6.Synthesis example 5, compound 7 synthetic.
The compound that obtains in 40 parts of synthesis examples 4 is dispersed in 500 parts of water, adds 15 parts of crystal copper sulphate and 10 parts of monoethanolamines, heat and reacted 10 hours at 95 ℃.Make reactant liquor saltout and filter by adding sodium chloride, obtain the copper complex salt dyestuff (sodium salt) of compound 7.Synthesis example 6, compound 8 synthetic.
By replace surely with paracresol in the synthesis example 4 using 2, the 5-dimethoxyaniline obtains the water-soluble dye (sodium salt) of compound 8.
Embodiment 1
The polyvinyl alcohol (PVA) of 75 micron thickness is 45 ℃ and contains dyestuff that concentration is 0.03% synthesis example 1 gained compound 1 and concentration is to soak 4 minutes in the aqueous solution of 0.1% sodium sulphate in temperature.This film is stretched 5 times in 50 ℃ 3% boric acid aqueous solution, and when keeping extended configuration, wash with water and drying, obtain a kind of polarizing coating.The gained polarizing coating has the maximum absorption wavelength of 550nm, even this polarizing coating also has the polarization property of height and shows long permanance under high temperature and super-humid conditions.
Embodiment 2
The polyvinyl alcohol (PVA) of 75 micron thickness is 45 ℃ and contains dyestuff that concentration is 0.03% synthesis example 3 gained compounds 3 and concentration is to soak 4 minutes in the aqueous solution of 0.1% sodium sulphate in temperature.This film is stretched 5 times in 50 ℃ 3% boric acid aqueous solution, and when keeping extended configuration, wash with water and drying, obtain a kind of polarizing coating.The gained polarizing coating has the maximum absorption wavelength of 630nm, even this polarizing coating also has the polarization property of height and shows long permanance under high temperature and super-humid conditions.
Embodiment 3
The polyvinyl alcohol (PVA) of 75 micron thickness is 45 ℃ and contains the dyestuff that concentration is 0.04% synthesis example 1 gained compound 1 in temperature, 0.03% C.I. direct orange 39, disclosed dyestuff among 0.04% the embodiment 1 by following structural (8) expression by day disclosure special permission communique No.12606/1991, disclosed dyestuff among 0.03% the embodiment 38 by following structural (9) expression by day disclosure special permission communique No.156759/1985, with soaked 4 minutes in the aqueous solution of 0.1% sodium sulphate.This film is stretched 5 times in 50 ℃ 3% boric acid aqueous solution, and when keeping extended configuration, wash with water and drying, obtain a kind of polarizing coating.The gained polarizing coating is a muted color, even and also have the polarization property of height and show long permanance under high temperature and super-humid conditions.
Embodiment 4
Is that 45 ℃ and the concentration that contains gained among the synthesis example 1-3 are to soak 4 minutes in the aqueous solution of the dyestuff, 0.03% C.I. direct orange 39 of the dyestuff of dyestuff, 0.04% compound 2 of 0.03% compound 1 and 0.04% compound 3 and 0.1% sodium sulphate with the polyvinyl alcohol (PVA) of 75 micron thickness in temperature.This film is stretched 5 times in 50 ℃ 3% boric acid aqueous solution, and when keeping extended configuration, wash with water and drying, obtain a kind of polarizing coating.The gained polarizing coating is a muted color, even and also have the polarization property of height and show long permanance under high temperature and super-humid conditions.
Embodiment 5
The polyvinyl alcohol (PVA) of 75 micron thickness is 45 ℃ and contains dyestuff that concentration is 0.03% synthesis example 4 gained compounds 6 and concentration is to soak 4 minutes in the aqueous solution of 0.1% sodium sulphate in temperature.This film is stretched 5 times in 50 ℃ 3% boric acid aqueous solution, and when keeping extended configuration, wash with water and drying, obtain a kind of polarizing coating.The gained polarizing coating has the maximum absorption wavelength of 615nm, even this polarizing coating also has the polarization property of height and shows long permanance under high temperature and super-humid conditions.
Embodiment 6
The polyvinyl alcohol (PVA) of 75 micron thickness is 45 ℃ and contains dyestuff that concentration is 0.03% synthesis example 5 gained compounds 7 and concentration is to soak 4 minutes in the aqueous solution of 0.1% sodium sulphate in temperature.This film is stretched 5 times in 50 ℃ 3% boric acid aqueous solution, and when keeping extended configuration, wash with water and drying, obtain a kind of polarizing coating.The gained polarizing coating has the maximum absorption wavelength of 665nm, even this polarizing coating also has the polarization property of height and shows long permanance under high temperature and super-humid conditions.
Embodiment 7
Is that 45 ℃ and the dyestuff, 0.03% C.I. direct orange 39,0.03% the C.I. that contain the compound 8 of gained in dyestuff that concentration is the compound 7 of gained in 0.05% the synthesis example 5,0.04% the synthesis example 6 directly soaked 4 minutes in the aqueous solution of red 81 and 0.1% sodium sulphate with the polyvinyl alcohol (PVA) of 75 micron thickness in temperature.This film is stretched 5 times in 50 ℃ 3% boric acid aqueous solution, and when keeping extended configuration, wash with water and drying, obtain a kind of polarizing coating.The gained polarizing coating is a muted color, even and also have the polarization property of height and show long permanance under high temperature and super-humid conditions.
Embodiment 8
With the polyvinyl alcohol (PVA) of 75 micron thickness temperature be 45 ℃ and contain dyestuff that concentration is the compound 7 of gained in 0.05% the synthesis example 5,0.03% C.I. direct orange 39,0.03% C.I. directly red 81 dyestuffs, 0.04% by the aqueous solution described in the embodiment 1 of day disclosure special permission communique No.218610/1999 by the sodium sulphate of the dyestuff of following structural (10) expression and 0.1% in soaked 4 minutes.This film is stretched 5 times in 50 ℃ 3% boric acid aqueous solution, and when keeping extended configuration, wash with water and drying, obtain a kind of polarizing coating.The gained polarizing coating is a muted color, even and also have the polarization property of height and show long permanance under high temperature and super-humid conditions.
Embodiment 9
The polyvinyl alcohol (PVA) of 75 micron thickness is 45 ℃ and contains dyestuff that concentration is 0.03% synthesis example 1 gained compound 1 and concentration is to soak 4 minutes in the aqueous solution of 0.1% sodium sulphate in temperature.This film is stretched 5 times in 50 ℃ 3% boric acid aqueous solution, and when keeping extended configuration, wash with water and drying, obtain a kind of polarizing coating.By a kind of TAC film (80 microns of thickness usefulness PVA type bonding agent on the surface of gained polarizing coating is bonding, product brand is called 80 UV TAC, produce by sensitive film company of Fuji), but and, obtain a kind of polarization plates (colored polarization plates) at the bonding a kind of film that makes by UV (ultraviolet ray) the curing type hard conating that on the one side of TAC film, forms about 10 micron thickness of the another side of described polarizing coating.Use the acrylic ester type bonding agent has adhesive phase with formation colored polarization plates in the one side of this polarization plates, and use a kind of AR (antireflection) overbrushing layer by vacuum vapor deposition in the outside of hard conating, be cut into 30-40 millimeter size, and its one side that is adhered in suitable size had on the transparency glass plate of AR layer, obtain the colored polarization plates (green channel that is used for liquid crystal projection apparatus) of the AR of having stilt of the present invention.The colored polarization plates of present embodiment has the maximum absorption wavelength (λ max) of 550nm, and the average penetrability of veneer is 42%, and the average penetrability of crossing condition is smaller or equal to 0.2% under the 500-580nm, and the average penetrability of crossing condition is 80% under the 630-780nm.
Embodiment 10
Use synthesis example 1 (b) gained compound 16 dyestuffs, make polarizing coating continuously, colored polarization plates and have the colored polarization plates (green channel that is used for liquid crystal projection apparatus) of AR stilt according to the same procedure of embodiment 9.The colored polarization plates of present embodiment has the maximum absorption wavelength (λ max) of 550nm, and the average penetrability of veneer is 42%, and the average penetrability of crossing condition is smaller or equal to 0.2% under the 500-580nm, and the average penetrability of crossing condition is 80% under the 630-780nm.
Embodiment 11
Use 0.04% synthesis example 1 gained compound, 1 dyestuff and 0.02% C.I. direct orange 39, make polarizing coating continuously, colored polarization plates and have the colored polarization plates (green channel that is used for liquid crystal projection apparatus) of AR stilt according to the same procedure of embodiment 9.The colored polarization plates of present embodiment has 42% the average penetrability of veneer, and the average penetrability of crossing condition is smaller or equal to 0.2% under the 500-580nm, and the average penetrability of crossing condition is 80% under the 630-780nm.Industrial applicibility
Owing to contain to compare with the polarization plates of using iodine and have high polarization property and superior durability according to the polarization plates of water-soluble dye of the present invention or its copper complex salt compound, therefore be applicable to the plurality of liquid crystals display, be specially adapted to the display of vehicle-mounted purposes, be used for the colored polarization plates of green channel of liquid crystal projection apparatus and the all-environment industrial instrumentation that is used for high polarization property of needs and permanance.

Claims (8)

1. polyvinyl alcohol (PVA) type polarizing coating, contain water-soluble dye or its copper complex salt dyestuff by following general formula (1) expression of free sour form at the substrate that is used for this polarizing coating:
Figure A0081009600021
Wherein A represents following general formula (2)
Figure A0081009600022
B represents following general formula (4) when A represents general formula (2);
Figure A0081009600023
And n is 1, the R in the general formula (4) 5Expression amino or hydroxyl, perhaps
A represents following general formula (3)
Wherein X represents nitro or amino, and B represents following general formula (5) when A represents general formula (3);
And n is 0 or 1, the R in the general formula (5) 6Expression hydrogen atom, hydroxyl, replacement or unsubstituted amino, methyl, ethyl, methoxy or ethoxy, R 7Expression hydrogen atom, hydroxyl, replacement or unsubstituted amino, methyl, ethyl, methoxy or ethoxy, R 1, R 2, R 3, R 4Represent hydrogen atom, methyl, ethyl, methoxyl, ethoxy and acetylamino independently of one another, its precondition be when n be 1, when A represents that general formula (2) and B represent general formula (4), get rid of all R 1, R 2, R 3And R 4All be the situation and the R of methyl or methoxy 1And R 3Be methyl and R 2And R 4Situation for methoxyl.
2. one kind as the defined polyvinyl alcohol (PVA) type of claim 1 polarizing coating, and this polarizing coating contains at least a water-soluble dye or its copper complex salt and at least a organic dyestuff that is different from above-mentioned dyestuff by general formula (1) expression.
3. polyvinyl alcohol (PVA) type polarization plates, this polarization plates contains a kind of diaphragm on the surface as any one the defined polyvinyl alcohol (PVA) type polarizing coating in claim 1 or 2.
4. polyvinyl alcohol (PVA) polarizing coating that is used for the green channel of liquid crystal projection apparatus, the substrate that is used for polarizing coating contain free sour form by the water-soluble dye of following general formula (6) expression and have more than or equal to 520nm and less than the maximum absorption wavelength (λ max) of 580nm:
Figure A0081009600031
R wherein 8, R 9, R 10And R 11Represent hydrogen atom, methyl, ethyl, methoxyl, ethoxy and acetylamino independently of one another, R 12Expression hydrogen atom, amino or hydroxyl.
5. polyvinyl alcohol (PVA) polarizing coating that is used for the green channel of liquid crystal projection apparatus, this polarizing coating contain the water-soluble dye and at least a organic dyestuff that is different from above-mentioned dyestuff of at least a general formula (6) expression by as defined in claim 4.
6. one kind as claim 4 or the 5 defined polyvinyl alcohol (PVA) polarization plates that are used for the green channel of liquid crystal projection apparatus, and wherein the average penetrability of the crossing condition when 630-780nm is more than or equal to 60%.
7. polyvinyl alcohol (PVA) polarization plates that is used for the green channel of liquid crystal projection apparatus, this polarization plates contains a kind of diaphragm on the surface of as defined in claim 4 polyvinyl alcohol (PVA) type polarizing coating.
8. color liquid crystal projector, this projector partly contains as defined in claim 7 polarization plates at green channel.
CNB008100969A 1999-07-14 2000-07-12 Polarizer comprising dye Expired - Lifetime CN1175289C (en)

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JP211148/99 1999-07-26
JP21114899A JP4162334B2 (en) 1999-07-26 1999-07-26 Dye-type polarizing film
JP211148/1999 1999-07-26
JP23405899A JP4162336B2 (en) 1999-08-20 1999-08-20 Dye-type polarizing film
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JP2003064276A (en) * 2001-08-27 2003-03-05 Sumitomo Chem Co Ltd Azo compound or its salt and dye-based polarizing film containing them
US8576485B2 (en) 2001-05-14 2013-11-05 The Hong Kong University Of Science And Technology Photo-induced dichroic polarizers and fabrication methods thereof
US7070913B2 (en) * 2001-05-14 2006-07-04 The Hong Kong University Of Science And Technology Photo-induced dichroic polarizers and fabrication methods thereof
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US7931702B2 (en) 2006-06-01 2011-04-26 Nippon Kayaku Kabushiki Kaisha Azo compound and salt thereof, and dye-containing polarizing film comprising the compound or salt
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Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59145255A (en) 1983-02-07 1984-08-20 Nippon Kayaku Co Ltd Water-soluble disazo compound
JPS60156759A (en) 1984-01-25 1985-08-16 Nippon Kayaku Co Ltd Water-soluble disazo compound
JPS60168743A (en) 1984-02-14 1985-09-02 Nippon Kayaku Co Ltd Colored polyvinyl alcohol film
US5084807A (en) * 1986-08-22 1992-01-28 U.S. Philips Corporation Illumination system for LCD projection television
JPS63189803A (en) 1987-02-03 1988-08-05 Nippon Kayaku Co Ltd Polarizing film
US4749259A (en) * 1987-05-15 1988-06-07 Hughes Aircraft Company Liquid crystal image projection with multicolor prepolarizing system
JPH0813932B2 (en) 1988-06-14 1996-02-14 日本化薬株式会社 Water-soluble azo dye and polarizing film containing the same
US5272259A (en) * 1988-12-23 1993-12-21 Bayer Aktiengesellschaft Stilbene dyestuffs and light-polarizing films or sheets containing stilbene
JP2622748B2 (en) 1989-06-12 1997-06-18 日本化薬株式会社 Water-soluble azo dye and polarizing film containing the same
JPH0378703A (en) * 1989-08-23 1991-04-03 Nippon Kayaku Co Ltd Polarizing plate
JPH04247404A (en) 1991-02-01 1992-09-03 Nippon Kayaku Co Ltd Liquid crystal projection type display
EP0549342B1 (en) * 1991-12-26 1999-03-10 Mitsui Chemicals, Inc. Water-soluble azo dyes and polarizing films using the dyes
JP3205096B2 (en) 1991-12-26 2001-09-04 三井化学株式会社 Water-soluble azo dye and polarizing film using the dye
US5423100A (en) * 1992-08-26 1995-06-13 Mitsui Toatsu Chemicals, Inc. Water-soluble azo compounds and polarizing films using the compounds
US5618868A (en) * 1993-04-21 1997-04-08 Mitsui Toatsu Chemicals, Inc. Polarizing film of a hydrophilic polymer film containing a novel azo compound
US5639809A (en) * 1994-06-22 1997-06-17 Mitsui Toatsu Chemicals, Inc. Azo compounds and polarizing films using the compounds
JP3661238B2 (en) 1994-09-16 2005-06-15 住友化学株式会社 Tetrakisazo compounds and their use in polarizing films
US5753145A (en) * 1995-06-02 1998-05-19 Hoecst Celanese Corp. Polarizer films with high thermal and hygroscopic stability
JPH10259311A (en) * 1997-03-19 1998-09-29 Sumitomo Chem Co Ltd Azo compound and dye-based polarizing film containing the same
JP4049229B2 (en) * 1998-01-30 2008-02-20 日本化薬株式会社 New polarizing film
JP3881175B2 (en) * 1998-12-18 2007-02-14 日本化薬株式会社 Color polarizing plate with support for liquid crystal projector and color liquid crystal projector
TW572970B (en) * 2000-11-27 2004-01-21 Sumitomo Chemical Co Polyazo compound or salt thereof and dye-based polarization film containing the same

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